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Hydrogenation of 4-chloronitrobenzenes over palladium and platinum catalysts supported on beta zeolite and γ-alumina

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Abstract

Liquid-phase hydrogenation of 4-chloronitrobenzene (4-CNB) to 4-chloroaniline (4-CAN) under mild reaction conditions (0.6 MPa, 25 °C, methanol-diethyl ether, 1:1 vol.) over palladium and platinum catalysts containing 1 mass% of metal supported on beta zeolite (M/B) or γ-alumina (M/A) was studied. The catalysts were prepared by the incipient wetness method using amino nitrate complexes and hydrogen as the reducing agent. SEM, adsorption–desorption nitrogen isotherms, XRD, TEM, and hydrogen chemisorption techniques were used for their characterization. The techniques employed revealed the presence of relatively large metal particles (approximately 15 nm; about 3% of metal dispersion). Stability of the catalysts during the hydrogenation was high; no catalyst changes were observed after two recycle runs. Hydrogenation over M/A catalysts was found to be faster than that over M/B catalysts in the methanol–diethyl ether mixture. Selectivity of only about 75% to 4-CAN was achieved over the M/A catalyst in methanol. Positive effect of the acid support (beta zeolite) and low polarity of the reaction environment (diethyl ether) are reflected in the high selectivity to 4-CAN; of about 99% at virtually 100% conversion of 4-CNB.

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Left: adopted from data published by Arjunan et al. (2012), right: adopted from data published by Sundaraganesan et al. (2009)

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Abbreviations

AC:

Activated carbon

Al-PILC:

Al-pillared clay

AN:

Aniline

ASMA:

Amino poly[styrene-co-maleic anhydride]

B:

Benzene

BET:

Brunauer, Emmet, and Teller

4-CAN:

4-Chloroaniline

CHAN:

Cyclohexane

ClPhNO:

Chloronitrosobenzene

ClPhHNOH:

N-chloro-phenylhydroxylamine

CN:

Carbon nitride

4-CNB:

4-Chloronitrobenzene

CNT:

Carbon nanotubes

DABP:

4,4′-Diaminobiphenyl

DETE:

Diethyl ether

DMF:

Dimethylformamide

DR:

Dubinin–Radushkevich

DOX:

1,4-Dioxane

EG:

Ethylene glycol

EtOAc:

Ethyl acetate

EtOH:

Ethanol

FTIR:

Fourier-transform infrared spectroscopy

GO:

Graphite oxide

HDC:

Hydrodechlorination

HDN:

Hydrodenitrogenation

HPLC:

High-performance liquid chromatography

M/A:

1 mass% of metal supported on γ-alumina

M/B:

1 mass% of metal supported on beta zeolite

MeOH:

Methanol

MC:

Mesoporous carbon

MS:

Mesoporous silica

NB:

Nitrobenzene

NTO:

Nitrotoluene

NAN:

Nitroaniline

NAS:

Nitroanisole

NMR:

Nuclear magnetic resonance

NTs:

Nanotubes

Rec.:

Number of repetitions with the same catalyst

SAED:

Selective electron diffraction

SEM:

Scanning electron microscopy

TEM:

Transmission electron microscopy

THF:

Tetrahydrofurane

TMB:

Trimethylbenzene

TOFH2 :

Turn over frequencies (molH2 mol −1metal s−1)

TOFs,H2 :

Turn over frequencies with respect to the metal surface (molH2 m−2 s−1)

Tol:

Toluene

TPD:

Temperature-programmed desorption

W:

Water

XRD:

X-ray diffraction

XPS:

X-ray photoelectron spectroscopy

C :

coefficient in the BET isotherm

d :

Average size of metal particles (nm)

d H2,CHS :

Average size of metal particles estimated from H2 sorption (nm)

d TEM :

Average size of metal particles estimated from TEM (nm)

d s,TEM :

Average size of metal particles estimated from TEM with respect to the surface (nm)

d V,TEM :

Average size of metal particles estimated from TEM with respect to the volume (nm)

d XRD :

Average size of metal particles estimated from XRD (nm)

D M :

Dispersion of metal (%)

D hkl :

Lattice parameter (nm)

f H2,M :

Factor expressing number of metal atoms interacting with hydrogen molecule

K:

The Scherrer’s constant (usually 0.9)

m cat :

Mass of a catalyst (g)

n CNB,0 :

Moles of x-CNB in the starting reaction mixture (mol)

n CNB,t :

Moles of x-CNB in the reaction mixture at time t (mol)

n H2,Chs :

Moles of H2 chemisorbed on catalyst sample (mol g−1)

n H2,r :

Moles of H2 consumed in the hydrogenation process (mol)

n Y :

Moles of component “Y” in the reaction mixture (mol)

P :

Polarity of a solvent (Pwater = 100)

s M :

Specific surface of metal particles (m2 g−1)

s A,M :

Surface equivalent of one metal atom (m2)

S Y :

Selectivity to compound “Y” (%)

t :

Time (s)

T FP :

Flash point temperature (°C)

T AI :

Autoignition temperature (°C)

v a :

Adsorbed amount expressed in the liquefied form (cm3 g−1)

V mi :

Volume of micropores (cm3 g−1)

w M :

Content of the metal in the dry catalyst (wt%)

x :

Relative pressure (x = p/ps)

x H2,25°C :

Mole fraction of H2 at 25 °C and 101.325 kPa

X CNB :

Conversion of chloronitrobenzene (%)

ε r :

Relative permittivity (dielectric constant)

Δ M :

Loose of the metal content as a portion of the initial amount of metal (%)

δ :

Solubility parameter

\(\overline{\delta }\) :

Average error

λ:

Wavelength of the X-ray used for the XRD (nm)

ρ :

Density (kg m−3)

η :

Dynamic viscosity (cP)

μ :

Dipole moment (D)

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Acknowledgements

This publication is a result of the project implementation: Hydrogenation in the Liquid Phase, ITMS: 26,220,220,144, supported by the Research & Development Operational Programme funded by the ERDF.

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Authors and Affiliations

  1. Institute of Organic Chemistry, Catalysis and Petrochemistry, Slovak University of Technology in Bratislava, Radlinského 9, 812 37, Bratislava, Slovakia

    Milan Králik, Dana Gašparovičová, Mária Turáková & Zuzana Vallušová

  2. VUCHT a.s, Areal Duslo a.s, 927 03, Šaľa, Slovakia

    Milan Králik, Jozef Balko, Peter Major & Milan Kučera

  3. SLOVNAFT, a.s, Vlčie hrdlo 1, 824 12, Bratislava, Slovakia

    Mária Turáková

  4. Faculty of Metallurgy, Technical University of Košice, Letná 9, 042 00, Košice, Slovakia

    Pavel Puliš & Ondrej Milkovič

Authors
  1. Milan Králik
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  2. Dana Gašparovičová
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  3. Mária Turáková
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  4. Zuzana Vallušová
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  5. Jozef Balko
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  6. Peter Major
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  7. Milan Kučera
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  8. Pavel Puliš
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  9. Ondrej Milkovič
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Correspondence to Milan Králik.

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Králik, M., Gašparovičová, D., Turáková, M. et al. Hydrogenation of 4-chloronitrobenzenes over palladium and platinum catalysts supported on beta zeolite and γ-alumina. Chem. Pap. 73, 397–414 (2019). https://doi.org/10.1007/s11696-018-0589-1

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  • DOI: https://doi.org/10.1007/s11696-018-0589-1

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